gboneu
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4-Nitrochlorobenzene synhtesis
Hello everyone, i want to make 4-nitrochlorobenzene by chlorination of nitrobenzene (is what i have) i've tried a few times but cant get anything. I
dissolve 3,2ml of nitrobenzene in ethanol (95%) and pass dry chlorine gass with iron wool to make FeCl3 insitu. HCl wass produce and the reaction was
carry out at 45ºC. I had a 2 layer produced and when they mix up (adding a little bit of EtOH) but nothing crystalized out, i cool the solution out
and some crystals precipitated but was nothing- I dont know what to do. I don't want to use Chloroform because i dont know if CCl4 is going to be
produce. And i dont have it in abundnace (It's expensive here (fuck)) 4-chloronitrobenzene is not verry soluble in EtOH and i know that EtOH react's
with chlorine but i didn's think it would be so bad- What can i do ? Could water and nitrobenzene be used in emulsion (Hard stirring) ?? Does someone
did it before ?
If i can use walter i could make the chlorine with TCCA adding HCL dropwise ... i think ...
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gdflp
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You will not be able to make 4-chloronitrobenzene in any appreciable amounts using this method because an aromatic nitro group is strongly
deactivating, and thus a meta-director. In addition, ethanol is a horrible solvent for chlorination for two reasons, namely that it does react with
chlorine and the fact that your product(3-chloronitrobenzene in this case) is soluble in ethanol. Nitration of chlorobenzene is the standard method
of preparing your target compound.
For future posting, post unreferenced material in <b>Beginnings</b>.
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Nicodem
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Thread Moved
3-6-2016 at 13:12 |
gboneu
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Thank's long time no posting-
Whell but what can i do ? I have nitrobenzene in my lab. solvent's like perchloroethylene, chloroform,methanol, would work ?
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gdflp
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It is not possible to chlorinate nitrobenzene to 4-chloronitrobenzene under any conditions amenable to an amateur. The simplest way you can do it I
mentioned in my previous post. You could reduce nitrobenzene to aniline, do a Sandmeyer to get chlorobenzene, then nitrate to get your target
product, but that is somewhat roundabout. If nitrobenzene is the only aromatic compound you have access to, that's the only way you can do it.
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PHILOU Zrealone
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Alternatively you could reduce nitrobenzene to aminobenzene (aniline), then monohalogenate it, isolate p-chloroaniline and then do a Sandmeyer
conversion of the diazonium salt into a nitro yielding your final product!
C6H5-NO2 -red-> C6H5-NH2
H2N-C6H5 --1 eq Cl2-> ClH3N-C6H4-Cl (ortho and para)
p-ClH3N-C6H4-Cl -NaNO2/Cu-> O2N-C6H4-Cl + NaCl + H2O + N2
PH Z (PHILOU Zrealone)
"Physic is all what never works; Chemistry is all what stinks and explodes!"-"Life that deadly disease, sexually transmitted."(W.Allen)
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gboneu
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thanks everyone, i'm afraid that i'd tried the synthesis of aniline but i cant get good yields, add to that that the nitrobenzene i have is very
expensive and i cant buy any more never again (ok maybe some day) my best yield was with the zinin reaction up to 50% but no more- i will se what i
can do thanks 
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CuReUS
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You could do this :
1.nitrobenzene to chlorobenzene - http://pubs.acs.org/doi/abs/10.1021/jo00247a042
2.chlorobenzene to 4-nitrochlorobenzene- http://www.tandfonline.com/doi/full/10.1081/SCC-120014967
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gboneu
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heyy CuReUS Thank's !! But phosphorus pentachloride is IMPOSSIBLE for me. In Argentina where i Live Such compounds are impossible to get
 Fuck my city, fuck my country, fuck everything... And Aniline hurt lik a litter
for $500 u$s (here's in Pesos not in Dollars bur it hurt's just like it) I gess i will have to get aniline, And Sulfuric acid is prohibited. Yes i
know. Chemistry is awesome here but thank's there are interesting articles =)
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CuReUS
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If you are getting aniline,then you could selectively monochlorinate it using this method that Philou found -http://www.ncbi.nlm.nih.gov/pmc/articles/PMC3388862/
after that,you can oxidise the NH2 to NO2 like this -http://pubs.acs.org/doi/abs/10.1021/jo00285a027
But I am surprised as to why there are so many restrictions in argentina ? What are the people up to ?
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PHILOU Zrealone
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The document is already requested in request document folder.
Once available, I'll post the link here.
PH Z (PHILOU Zrealone)
"Physic is all what never works; Chemistry is all what stinks and explodes!"-"Life that deadly disease, sexually transmitted."(W.Allen)
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CuReUS
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Quote: Originally posted by gboneu  | | i'm afraid that i'd tried the synthesis of aniline but i cant get good yields... my best yield was with the zinin reaction up to 50% but no more
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why don't you try the reduction using sodium dithionite,its an easy and high yielding way
http://www.orgsyn.org/demo.aspx?prep=CV3P0069
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PHILOU Zrealone
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Et voilà! Here is the requested document, thanks to Solo.
Requested documents in reference section by PHILOU Zrealone
PH Z (PHILOU Zrealone)
"Physic is all what never works; Chemistry is all what stinks and explodes!"-"Life that deadly disease, sexually transmitted."(W.Allen)
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